AU2015210692B2 - Anti-glare, texture coating for packaging - Google Patents
Anti-glare, texture coating for packaging Download PDFInfo
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- AU2015210692B2 AU2015210692B2 AU2015210692A AU2015210692A AU2015210692B2 AU 2015210692 B2 AU2015210692 B2 AU 2015210692B2 AU 2015210692 A AU2015210692 A AU 2015210692A AU 2015210692 A AU2015210692 A AU 2015210692A AU 2015210692 B2 AU2015210692 B2 AU 2015210692B2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/006—Patterns of chemical products used for a specific purpose, e.g. pesticides, perfumes, adhesive patterns; use of microencapsulated material; Printing on smoking articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/006—Anti-reflective coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/408—Matt, dull surface
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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Abstract
An anti-glare, texture coating is described. The coating comprises an emulsion comprising (a) water, (b) a first particle comprising particles having an average particle size of greater than 0 but less than 10 microns and comprising acrylic beads, (c) an acrylic-based carrier and (d) a second particle comprising particles having an average particle size of from about 10 microns to about 125 microns and comprising polyamide, polyethylene, polypropylene, polytetrafluoroethylene or combinations or combinations of such. The combination of the water, the first particle and the acrylic-based carrier comprises from about 75 % to about 95 % by weight of the coating, and the second particle comprises from about 5 % to about 25 % by weight of the coating. Also described is a packaging material comprising (a) the coating and (b) a substrate comprising metal, glass, paper, plastic or thermoplastic. Further described is a method of rotogravure printing the coating to the substrate.
Description
BACKGROUND OF THE INVENTION
This present application describes a coating that imparts anti-glare and texture properties to packaging. Such coating includes water, an acrylic carrier, acrylic particles and other organic particles.
Coatings are used in various industries. For example, US Patent 6,730,388 discloses a high viscosity, cured resin coating applied to a flooring substrate via air knife, roll coater, spray coating or curtain coating. The cured resin coating is primarily non-aqueous (comprising only minute concentrations or water) and may comprise a flatting agent comprising 5-micron-sized nylon particles and a plurality of textureproducing particles comprising 60-micron-sized nylon particles.
In general, in some industries, coatings may comprise a liquid base, a resin base, an additive or additives and a reducer/thinner. The liquid base may be waterbased or solvent-based, (As used in this context, a water-based liquid base is distinct from a solvent-based liquid base, even though water is chemically considered a solvent.) The resin base may be any one or a combination of various solids-containing materials that impart properties and benefits such as texture, heat resistance, abuse resistance (e.g., scuff and/or abrasion resistance), opacity, gloss, anti-glare, etc. The additive or additives may be liquid or solid and may further contribute to the properties and benefits. The reducer/thinner is a liquid used to adjust the viscosity of the coating to enable efficient application of the coating and may be water-based, solvent-based or a blend of water-based and solvent-based.
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PCT/US2015/014171
Coatings are used on packaging to impart various properties and benefits to packaging. For example, US Patent Application Publication 2012/0015145 discloses a coating including pigments and a binder to create a matter varnish layer. The pigments may be polyurethane microbeads, and the binder may be based on acrylic.
What is needed is a cost-effective coating that imparts anti-glare and texture properties to packaging without negatively impacting other properties and benefits.
BRIEF SUMMARY OF THE INVENTION
This need is met by the coating described in the present application. A first embodiment describes a coating comprising an emulsion comprising (a) water, (b) a first particle comprising particles having an average particle size of greater than 0 but less than 10 microns and comprising acrylic beads, (c) an acrylic-based carrier and (d) a second particle comprising particles having an average particle size of from about 10 microns to about 125 microns or from about 25 microns to about 125 microns or from about 80 microns to about 110 microns and comprising polyamide, polyethylene, polypropylene, polytetrafluoroethylene or combinations of such. The combination of the water, the first particle and the acrylic-based carrier comprises from about 75 % to about 95 % or from about 80 % to about 90 % or from about 82 % to about 85 % by weight of the coating . The second particle comprises from about 5 % to about 25 % or from about 10 % to about 20 % or from about 15 % to about 18 % by weight of the coating. In some embodiments, the second particle may comprise particles having a first particle size and a second particle size. In some embodiments, the coating may also comprise a coreactant additive in an amount from 0 % to about 5 % by weight of the coating. The coating may be printable and may create an anti-glare, texture effect
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PCT/US2015/014171 on a packaging material in the absence of radiation curing. In some embodiments, the coating may have a viscosity of from about 50 to about 125 centipoise or from about 70 to about 125 centipoise.
in a second embodiment, a packaging material is described comprising a substrate comprising metal, glass, paper, plastic or thermoplastic and the coating described above. The packaging material may be food packaging. The packaging material may have an anti-glare, texture effect in the absence of radiation curing. In some embodiments of the second embodiment, the substrate may comprise a thermoplastic film or biaxially oriented polyethylene terephthalate. In some embodiments, the coating may be printable and may be flexographic printed or rotogravure printed.
In a third embodiment, a method of rotogravure printing a coating to substrate is described. This method comprises the steps of (a) preparing the coating described above, (b) using a rotogravure press to apply the coating to the substrate described above and (c) allowing the coated substrate to cure in the absence of radiation curing. In some embodiments, the method may further comprise adding reducer/thinner to the coating as needed to adjust coating viscosity to measure from about 50 centipoise to about 125 centipoise or from about 70 centipoise to about 125 centipoise and/or adding a coreactant additive to the coating in an amount from 0 % to about 5 % by weight of the coating. In some embodiments, the method may further comprise corona treating the substrate prior to using the rotogravure press to apply the coating to the substrate. In some embodiments, the method may further comprise applying ink to the substrate as either a surface print or reverse print prior to using the rotogravure press to apply the
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PCT/US2015/014171 coating to the substrate, if the method includes applying ink, the rotogravure press may then apply the coating on a surface over the ink if surface printed or on a surface without the ink if reverse printed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS 1 and 2 are SEM photographs of the surface of an embodiment of a packaging material according to the present application,
FIG. 3 is a SEM photograph of a sample stacked image of the surface of an embodiment of a packaging material according to the present application.
FIG 4 is a SEM height profile of an embodiment of a packaging material according to the present application.
FIGS 5-12 are SEM photographs of the surface of an embodiment of a packaging material according to the present application.
DETAILED DESCRIPTION OF THE INVENTION
With references io the embodiments described in the present application, in some embodiments, the coating may provide the package with the look and feel of traditional butcher paper or Kraft paper. The coating may be applied to various food or non-food packaging materials and substrates including but not limited to metal, glass, paper, plastic and thermoplastic by means known in the art. In one embodiment, the coating may be “printable” and may be applied to paper or thermoplastic substrates by coating or printing means known in the art. Such means include but are not limited to flexographic coating and printing and rotogravure coating and printing. As used throughout this present application and as known in the art, the term “printable” refers to a coating that is able to be printed on a substrate, as distinguished from a substrate that
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PCT/US2015/014171 is able to be printed with a coating. In same embodiments, the coating or printing means do not require energy curing, such as ultraviolet (UV) radiation or electron beam (e~beam) radiation. As such, thermoplastic webs to be coated or printed may be wider (e.g., greater than about 24 inches (about 61 centimeters)) than those requiring UV curing. As known in the art, UV curing is predominantly done on narrow webs of width less than about 24 inches (about 61 centimeters) As used throughout this present application, the term thermoplastic” refers to a polymer or polymer mixture that softens when exposed to heat and then returns to its original condition when cooled to room temperature. In general, thermoplastic materials may include natural or synthetic polymers and may be used in flexible, semi-rigid or rigid packaging, as known in the art.
In some embodiments, the anti-glare, texture coating described in this present application comprises a water-based liquid base, an anti-glare agent resin base, a texture agent additive, an optional coreactant additive and an optional water-based or water-based and solvent-based blend reducer/thinner.
The anti-glare agent is capable of reducing or eliminating glare. In general, an anti-glare agent addresses external sources of reflection (such as bright sunlight or high ambient lighting conditions) off a surface and the possible impact of the reflection, such as the impact on readability or general aesthetics. Anti-glare agents use diffusion mechanisms to disperse or otherwise break up the reflected light. Such diffusion mechanisms include but are not limited to (1) mechanical or chemical surface texturing and (2) minute particles suspended or otherwise incorporated into a liquid coating.
Non-limiting examples of anti-glare agents with particles (as suspensions or otherwise) include the following:
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PCT/US2015/014171 • resins particles, such as acrylic resin particles, cross-linked acrylic resin particles, polystyrene particles, cross-linked polystyrene particles, melamine resin particles, benzoguanamine resin particles and blends of such, as disclosed in US Patent 7,611,760;
» a mixture of two incompatible polymers, with different refractive indexes of individual polymer domains, such as polymethylmethacrylate and polystyrene, as disclosed in US Patent 6,939,576;
• water-soluble organic polymers such as polysaccharides and derivatives of such, including nonionic cellulose ethers (e.g,, ethyl hydroxyl cellulose), cationic cellulosic ethers (e.g,, quaternary ammonium modified cellulose ether) and polyglucosamines and derivatives of such, as disclosed in US Patent 7,703,456; and • hydrophilic polymers such as hydrophilic organic monomers or oligomers, prepolymers and copolymers derived from the group consisting of vinyl alcohol, Nvinylpyrrolidone, N-vinyl lactam, acrylamide, amide, styrenesulfonic acid, combination of vinylbutyral and N-vinylpyrrolidone, hydroxyethyl methacrylate, acrylic acid, vinylmethyl ether, vinylpyridylium halide, melamine, maleic anhydride/methyl vinyl ether, vinylpyridine, ethyleneoxide, ethyleneoxide ethylene imine, glycol, vinyl acetate, vinyl acetate/crotonic acid, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl ethyl cellulose, hydroxy propyl methyl cellulose, cellulose acetate, cellulose nitrate, starch, gelatin, albumin, casein, gum, alginate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol methacrylates (e.g., triethylene glycol methacrylate) and methacrylamides, N-alkyl methacrylamides
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PCT/US2015/014171 (e.g., N-methyl methacrylamide and N-hexyl methacrylamide), N,N-dialkyl methacrylamides (e.g., N,N-dimethyl methacrylamide and poly-N,N-dipropyl methacrylamide), N-hydroxyalkyl methacrylamide polymers (e.g., poly-N~methylol methacrylamide and poly-N-hydroxy ethyl methacrylamide), Ν,Ν-dihydroxyalkyl methacrylamide polymers (e.g., poly-N,N-dihydroxyethyl methacrylamide, ether polyols, polyethylene oxide, polypropylene oxide, polyvinyl ether, alkylvinyl sulfones, alkylvinyisulfone-acrylates and related compounds and a combination of any of the above, as disclosed in US Patent 7,008,979.
Further non-limiting examples of anti-glare agents include the Opulux™ Optical Finishes, such as Opulux™ 4903, Opulux™ 5000, and Opulux™ 5001, each available from The Dow Chemical Company (Midland, Michigan). In addition to anti-glare, the Opulux™ Finishes may provide heat resistance and abuse resistance not generally provided by matte coatings or matte varnishes. The Opulux™ Finishes (also referred to as overlacquers) are water-based, acrylic-based (such that they are water-resistant when dry) and include acrylic beads in combination with an acrylic-based carrier technology. As disclosed in the October 2012 Opulux™ Technical Overview from The Dow Chemical Company, the acrylic beads have a particle size of greater than 0 microns but less than 10 microns. As further disclosed in the October 2012 Opulux™ Technical Overview, the Opulux™ Finishes produce a soft, smooth, non-rough, nontextured, luxurious touch and feel for packaging and labels. When used in the coating described in this present application, the water of the Opulux™ Finish comprises the liquid base of the coating and the acrylic beads (also referred to as “first particle”) in combination with the acrylic-based carrier comprise the resin base of the coating. As
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PCT/US2015/014171 used throughout this present application, the term “acrylic” refers to thermoplastic polymers or copolymers of acrylic acid, methacrylic acid, esters of these acids or acrylonitrile, as defined in Hawley’s Condensed Chemical Dictionary, 14th Edition, 2001. As known in the art, acrylics (including acrylic beads/particles and acrylic-based carriers) are generally non-water soluble or water insoluble and, as such, form emulsions with water. Furthermore, as known in the art and as used throughout this present application, the term “emulsion” refers to a dispersion of droplets of one substance in another in which it is not soluble or in which it is insoluble.
In general, for the anti-glare, texture coating described in the present application, the combination of the liquid base and the resin base may comprise from about 75 % to about 95 % by weight of the coating or from about 80 % to about 90 % by weight of the coating or from about 82 % to about 85 % by weight of the coating or, more specifically, about 83.5 % by weight of the coating.
The anti-glare, texture coating also comprises a texture agent additive (also referred to as “second particle”) and, optionally, a coreactant additive. The texture agent additive may comprise organic compounds, particles or powders such as those comprising polyamide (PA), polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE) or combinations of such. In some embodiments, the texture agent may consist essentially of organic compounds, particles or powders, such that it does not comprise any effective amount of inorganic compounds, particles or powders such as talc (and other inorganic minerals), silica, titanium dioxide, metal, calcium salts such as calcium carbonate and calcium sulfate, sand, clay, diatomaceous earth or combinations of such. It is believed (without being bound by belief) that softer, §
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PCT/US2015/014171 compressible organic additives may allow for processing, coating and printing efficiencies in that they may be easier to wipe and not as harsh on equipment as compared to the traditional hard, coarse, abrasive inorganic additives. Additionally, as known in the art, such organic additives are non-water soluble or water insoluble. Nonlimiting examples of organic texture agent additives include the following:
• Nylotex 200, a finely micronized polyamide having a reported melting point of 218-
224 °C, a reported density at 25 °C of 1.14 g/cc, a reported mean particle size of 30SO microns and a reported maximum particle size of 74 microns, available from Micro Powders, Inc. (Tarrytown, New York);
• Nylotex 140, a finely micronized polyamide having a reported melting point of 218-
224 °C, a reported density at 25 °C of 1.14 g/cc, a reported mean particle size of 4565 microns and a reported maximum particle size of 104 microns, available from Micro Powders, Inc. (Tarrytown, New York);
• Texture-UF, a crystalline polyethylene powder having a reported melting point of 144 °C, a reported specific gravity at 25 °C of 0.93, a reported slip ranking of 5, a reported abrasion ranking of 9 and a reported average particle size of 35 microns, available from Shamrock Technologies, Inc. (Newark, New Jersey);
• Texture-5378W, a crystalline polyethylene powder having a reported melting point of 144 °C, a reported specific gravity at 25 °C of 0.93, a reported slip ranking of 5, a reported abrasion ranking of 9 and a reported average particle size of 50 microns, available from Shamrock Technologies, Inc. (Newark, New Jersey);
• Texture-5380W, a crystalline polyethylene powder having a reported melting point of
144 °C, a reported specific gravity at 25 °C of 0.93, a reported slip ranking of 5, a
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PCT/US2015/014171 reported abrasion ranking of 9 and a reported average particle size of 65 microns, available from Shamrock Technologies, Inc. (Newark, New Jersey);
• Texture-5382W, a crystalline polyethylene powder having a reported melting point of 144 °C, a reported specific gravity at 25 °C of 0.93, a reported slip ranking of 5, a reported abrasion ranking of 9 and a reported average particle size of 80 microns, available from Shamrock Technologies, Inc. (Newark, New Jersey);
• Texture-5384-W, a crystalline polyethylene powder having a reported melting point of 144 °C, a reported specific gravity at 25 °C of 0.93, a reported slip ranking of 5, a reported abrasion ranking of 9 and a reported average particle size of 110 microns, available from Shamrock Technologies, Inc.. (Newark, New Jersey);
• Fluo 625CTX2, a micronized polytetrafluoroethylene having a reported softening point of greater than 316 0 C, a reported density at 25 ° C of 2.15 g/cc, a reported maximum particle size of 124.0 microns and a reported mean particle size of 20.025.0 microns, available from Micro Powders, Inc. (Tarrytown, New York);
• Fluo 625F, a micronized polytetrafluoroethylene having a reported softening point of greater than 316 * C, a reported density at 25 ° C of 2.2 g/cc, a reported maximum particle size of 44.0 microns and a reported mean particle size of 11.0-13.0 microns, available from Micro Powders, Inc. (Tarrytown, New York);
• Fluo 625F-H, a micronized polytetrafluoroethylene having a reported softening point of greater than 316 ° C, a reported density at 25 ° C of 2.2 g/cc, a reported maximum particle size of 96.0% < 44.0 microns and a reported mean particle size of 13.0-21.0 microns, available from Micro Powders, Inc. (Tarrytown, New York);
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PCT/US2015/014171 • Fluo 750TX, a micronized polytetrafluoroethylene having a reported softening point of 325-350 ° C; a reported density at 25 * C of 2.2 g/cc, a reported maximum particle size of 148 microns and a reported mean particle size of 20-30 microns, available from Micro Powders, Inc. (Tarrytown, New York);
» Fluo 850TX, a micronized polytetrafluoroethylene having a reported softening point of 340-350 ° C, a reported density at 25 * C of 2.2 g/cc, a reported maximum particle size of 148.0 microns and a reported mean particle size of 20.0-30.0 microns, available from Micro Powders, Inc. (Tarrytown, New York); and • Microtex 511, a micronized modified high molecular weight polytetrafluoroethylene having a reported softening point of greater than 316 0 C, a reported density at 25 0 C of 2.20 g/cc, a reported maximum particle size of 124.0 microns and a reported mean particle size of 20.0-25.0 microns, available from Micro Powders, Inc. (Tarrytown, New York).
Product literature further reports that both the Micro Powders Nylotex materials and the Shamrock Texture materials provide enhancements to and benefits with UV radiation systems (i,e., those that require radiation curing). Such product literature is silent regarding possible applications in non-UV radiation systems (Le., those that require no radiation curing). Additionally, product literature further reports that the Micro Powders polytetrafluoroethylene products are mainly used in combination with micronized waxes to achieve higher surface lubricity and anti-blocking properties.
The texture agent additive may comprise particles of from about 10 microns to about 125 microns in size or from about 25 microns to about 125 microns in size or from about 35 microns to about 110 microns in size or from about 50 microns to about 110
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PCT/US2015/014171 microns in size or from about 65 microns to about 110 microns in size or from about 74 microns to about 110 microns in size or from about 80 microns to about 110 microns in size. The texture agent additive may comprise from about 5 % to about 25 % by weight of the coating or from about 10 % to about 20 % by weight of the coating of from about 15 % to about 18 % by weight of the coating or, more specifically about 15 % by weight of the coating. Additionally, the texture agent additive may comprise particles of more than one size. As non-limiting examples, the texture agent additive may comprise a combination of about 25 % 110-micron size particles and about 75 % 80-micron size particles or a combination of about 66.7 % 80-micron size particles and about 33.3 % 65~micron size particles or a combination of about 66.7 % 65-micron size particles and about 33.3 % 50-micron size particles or a combination of about 33.3 % 50~micron size particles and about 66.7 % 35-micran size particles. (In each example above, the percent is a percent by weight of the texture agent additive.)
As described above, the anti-glare, texture coating may also comprise a coreactant additive. The coreactant additive, also known as a hardener, an external crosslinker, a crosslinker and/or a catalyst may be added to enable the coating to adhere, dry, cure and/or solidify and/or to contribute to abuse resistance. A non-limiting example of a coreactant additive is CR 9-101, available from The Dow Chemical Company (Midland, Michigan). In general, a coreactant additive may comprise from 0 % to about 5 % by weight of the coating or from about 1 % to about 3 % by weight of the coating or from about 1.5% to about 2.5 % by weight of the coating or, more specifically, about 1.5 % by weight of the coating.
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The anti-glare, texture coating may also comprise a reducer/thinner comprising water only or comprising a water/isopropyi alcohol blend. This reducer/thinner may comprise isopropyl alcohol in any amount from 0 % to about 20 % (such as, as nonlimiting examples, 0 % to about 15 %, 0 % to about 10 %, 0 % to about 5 %, etc.) by weight and water in any amount from about 80 % to 100 % (such as, as non-limiting examples, about 85 % to 100 %. about 90 % to 100 %, about 95 % to 100 %, etc.) by weight, where the percent is a percent by weight of the blend. As a blend, the reducer/thinner is a blend known in the art that may be added to a coating to adjust the viscosity of the coating to allow for efficient printing or other application. For rotogravure printing of a coating of the present application, the target viscosity may be from about 50 to about 125 centipoise (from about 15 to about 37 seconds on a Shell Cup #4) or from about 70 to about 125 centipoise (from about 21 to about 37 seconds on a Shell Cup #4) or from about 90 to about 107 centipoise (from about 27 to about 32 seconds on a Shell Cup #4).
The anti-glare, texture coating may also comprise additional coating additives. For example, the coating may comprise additives to affect the coefficient of friction (COF) to address sliding or skidding. Such additives may provide anti-skid properties or otherwise prevent sliding. A non-limiting example of an anti-skid additive is HYPOD™ 8501 Polyolefin Dispersion, available from The Dow Chemical Company (Midland, Michigan).
The anti-glare, texture coating may be produced as follows: The anti-glare agerrt is mixed with the texture agent. The viscosity is then measured, if the viscosity is not within a target range, the reducer/thinner (either water only or a water/isopropyi alcohol
WO 2015/117111
PCT/US2015/014171 biend as described above) is added in an amount known io a person of ordinary skill in the art. The combination is mixed and the viscosity is again measured. Once the viscosity is within the target range, the combination is trialed as known in the art for the coating or printing application. Adjustments (e.g., further additions of the reducer/thinner) are made as needed based on the quality of the trial. Once the quality of the trial is acceptable as known in the art, the optional coreactant additive may be mixed with the combination to form the coating..
Specific exampies of produced coatings (with weight percent of the coating listed) are reported in Table 1.
TABLE 1
Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
Opulux 4903 | 83.50 | 83.50 | 83.50 | 83.50 | 83.50 |
Texture-5384W Texture-5382W Texture-5380W | 3.00 12.00 | 15.00 | 10.00 5.00 | 10,00 | |
Texture-5378W | 5.00 | 5.00 | |||
Texture-UF | 10.00 | ||||
CR 9-101 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 |
As described above, the coating may be applied to a thermoplastic film via flexographic printing or coating or rotogravure printing or coating. As known in the art, when viewed under a printers loop, the edge of a coating applied to a substrate via flexographic printing / coating or flexography has a straight edge and the edge of a coating applied to a substrate via rotogravure printing /coating or gravure has a scalloped edge. With flexographic printing or coating or rotogravure printing or coating, the coating may be pattern-applied or flood coated. A non-limiting example of a thermoplastic fiim to which the coating may be applied is a monolayer film of 48-gauge biaxially oriented polyethylene terephthalate. Prior to the application of the coating, this
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PCT/US2015/014171 film may (or may not) be corona treated as known in the art. In one embodiment, a rotogravure press may apply ink to the optionally corona-treated side (for a surface print) or to the non-treated side (for a reverse print). The press then applies the coating to the optionally corona-treated side either over the ink (if surface printed) or without ink 5 (if reverse printed). As known, in the art, the press may use thermal forced air to dry the coated and optionally printed film. The resulting film may then be laminated (e.g,, via adhesive lamination, extrusion lamination or otherwise as known in the art) to another film, such as, as a non-limiting example, a barrier sealant film. A non-limiting example of a barrier sealant film is a 4-mil (102-micron) thick film having the general construction reported in Table 2.
TABLE 2
Weight % of Film
Layer 2
Layer 3
Layer 4 LayerS
Component
15.9
Layers
Layer?
Ultra low density polyethylene (ULDPE) Linear low density polyethylene (LLDPE) Processing aids___________________________
Ultra low density polyethylene (ULDPE)..................
Linear low density polyethylene (LLDPE)..............
Processing aids___________________________
Linear low density polyethylene (LLDPE) tie Tie concentrate___________________________
Ethylene vinyl alcohol (EVOH)_____________
Li near low density polyethylene j LLDPE) tie Tie concentrate___________________________
Ethylene vinyl acetate (EVA)______________
Poiybutene (P 8)__________________________
Ethylene vinyl acetate (EVA)______________
Processing aids
Weight % of Layer
......64,1......
34.3
1.6
............64.1.............
34.3
1.6
55.9
14.1
100.0
85.9
14.1
82.0
18.0
95.0
5.0
After adhesive lamination, the multilayer film with the anti-glare, texture coating is cured at room temperature for 24 hours. In one embodiment, the film is not subjected to is radiation curing in the form of UV radiation or e-beam radiation or otherwise or to any energy curing other than the thermal forced air of the press used to dry the coated and
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PCT/US2015/014171 optionally printed film. As the film is not subjected to UV radiation in this embodiment, the coating does not require a photo initiator.
When applied to a film, each of the coatings of Examples 1-5 reported in Table 1 provided heat resistance, abuse resistance and printebility based on tests known in the art. As evidence of heat resistance, each coated film released from a platen without sticking when placed in a heat sealer at 400 a F (204 5 C) at 40 psi (275.790 kPA) tor one second dwell time. As evidence of abuse resistance, each coated film did not lose any coating when scratched with a fingernail. As evidence of printability, each coated film printed without any known print defects (such as streaks, tails, clouds, etc.) as known in the rotogravure printing arts.
Additionally, various properties of the anti-glare, texture coating may be measured. These properties include but are not limited to gloss level and roughness/texture. Gloss level is a visual impression resulting from surface evaluation. The more direct light that is reflected, the higher the gloss level and vice versa. Gloss level (or specular reflection) may be measured via a glossmeter. The measurement values of a glossmeter relate to the amount of reflected light from a black glass standard with a defined refractive index, not to the amount of incident light. The measurement value for this defined standard is equal to 100 gloss units (calibration). Materials with a higher refractive index, such as uncoated thermoplastic films, may have measurement values above 100 gloss units (GU). As a result, for some applications, the gloss level may be documented as a percent reflection of illuminated light.
To determine a non-limiting example gloss level for an embodiment of the antiglare, texture coating of the present application, the gloss units for a film having the
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PCT/US2015/014171 coating of Example 2 and for the same film not having the coating were measured using a BYK-Gardner Glossmeter. The average reading at 60 degree for a film with the antiglare, texture coating was 2.4 gloss units, while the average reading at 60 degree for a film without the anti-glare texture coating was 123.6 gloss units, resulting in a gloss level 5 of 1.94%. According to product literature from BYK-Gardner, a material with 2.4 gioss units at 60 degree is considered a low gloss material.
Additional gloss units were measured for further embodiments of the anti-glare, texture coating of the present application. The gloss units for films having the coating of each of Examples 1-5 were measured as described above. The average gloss units at io 60 degree is reported in Table 3. (The reported average gloss units for each example is based on 15 readings. Statistically, the high value and low value for each of the 15 readings for each example cross over one another.) Using an average reading of 123.6 gloss units for a film without the anti-glare, texture coating, the gloss level in percentage (%) is also reported in Table 3.
is TABLE 3
Average | Gloss | |
Gloss | Level | |
Example | Units | (%) |
Example 1 | 3.6 | 2.91 |
Example 2 | 3.9 | 3.16 |
Example 3 | 3.8 | 3.07 |
Example 4 | 4.1 | 3.32 |
Example 5 | 3.9 | 3.16 |
Therefore, a film having the anti-glare, texture coating of the present application may have a gloss level of from 0 % to about 15 % or from 0 % to about 10 % or from 0 % to about 5 % or from about 1.5% to about 3.5 % or less than about 5 %.
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Texture may also be evaluated for the anti-glare, texture coating of the present application, A film having the coating of Example 1 was examined with a first light microscope / scanning electron microscope (SEM) (the “first SEM1'). The first SEM is Model 1645 from Amray, Inc. The first SEM uses Semicaps software for analysis. FIGS 1 and 2 are SEM photographs of the surface of an embodiment of a packaging material according to the present application, FIGS, 1 and 2 are cross-sections of the coated film with the first SEM at 1000 times magnification. FIG. 1 is a cross-section of an area of the coated film with higher distribution of acrylic beads (or “first particle from the anti-glare agent) and polyethylene particles (or “second particle from the texture agent). FIG. 2 is a cross-section of an area of the coated film with lower distribution of acrylic beads and polyethylene particles. Based on FIGS, 1 and 2, an example, nonlimiting measurement of the vertical distance between the highest peak and the deepest valley (also known as “Single Roughness Depth or “Surface Roughness Average” or RA) was estimated to be from about 0.15 mil (3.8 microns) to about 0.20 mil (5,1 microns).
Additional RA measurements for a film having the coating of Example 1 were obtained using a second scanning electron microscope (SEM) (the “second SEM”). The second SEM is a JSM-6010PLUS/LA Scanning Electron Microscope available from JEOL USA, Inc. (Peabody, Massachusetts). The second SEM uses Scandium software from Olympus for analysis. With the second SEM, RA was measured at low magnification (e.g., at 100 times magnification). Readings at 0 ° tilt and 7 ° tilt at 100 times magnification were stacked and combined for a three-dimensional profile to facilitate the determination of RA. FIG, 3 is a SEM photograph of a sample stacked
WO 2015/117111
PCT/US2015/014171 image of the surface of an embodiment of a packaging material according to the present application. For this embodiment, the RA between successive points of the film having the coating of Example 1 ranged from 0.43 microns to 5.08 microns and was, understandably, dependent on the track of the profile line. The Average RA was reported at 0.61 microns or approximately 1 micron. FIG 4 is a SEM height profile of an embodiment of a packaging material according to the present application. This height profile was determined at 7 ° tilt and 100 times magnification. It reports the vertical height above the surface across the width of the film having the coating of Example 1. For example at 200 microns from the edge of this film, the vertical height above the surface was approximately 19.5 microns.
FIG 5 is an SEM photograph of the surface of an embodiment of a packaging material according to the present application. FIG. 5 is a surface evaluation of a film having the coating of Example 1 with the first SEM at 50 times magnification. The larger, lighter particles, e.g., particles 500, were polyethylene particles, and measured approximately 70 microns in diameter; the smaller, darker particles, e.g., particles 550, were ink. Based on FIG.5, an example, non-limiting measurement of the distribution of polyethylene particles on this coated film surface was estimated to be about 600 particles per square centimeter. FIG. 6 is a SEM photograph of the surface of an embodiment of a packaging material according to the present application. FIG. 6 is a surface evaluation of a film having the coating of Example 1 with the first SEM at 500 times magnification. The large particle near the upper center was a polyethylene particle 600; the smaller particles distributed throughout were acrylic beads 650.
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FIG. 7 is a SEM photograph of the surface of an embodiment of a packaging material according to the present application. FIG. 7 is a surface evaluation of a film having the coating of Example 1 with the first SEM at a 60 degree tilt at 1000 times magnification. The larger bumps e.g., particles 700, were acrylic beads from the antiglare agent. Based on a ratio of 20 pm of film surface per, e.g., 23 millimeters (depending on size of image when printed or otherwise viewed) of picture (as described in legend 790 at the lower right corner), an example, non-limiting measurement of the diameter range for the majority of the acrylic beads was from about 1 micron to about 5 microns.
FIG. 8 is a SEM photograph of the surface of an embodiment of a packaging material according to the present application. FIG. 8 is a surface evaluation of a film having the coating of Example 1 with the second SEM at 0 degree tilt at 500 times magnification. The larger “bumps” (e.g., particle 810, particle 820, particle 830, particle 840) were, again, acrylic beads from the anti-glare agent. According to the second SEM, particle 810 had a diameter of about 9.7 microns, particle 820 had a diameter of about 8.4 microns, particle 830 had a diameter of about 5.0 microns and particle 840 had a diameter of about 6.4 microns. Based on FIG. 7 and FIG. 8, the acrylic beads in these embodiments had a particle size of greater than 0 microns but less than 10 microns. Also according to the second SEM, an example, non-limiting measurement of the distribution of acrylic beads on this coated film surface was estimated to be from about 700,000 particles per square centimeter to about 1,000,000 particles per square centimeter.
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FIG. 9 is a SEM photograph of the surface of an embodiment of a packaging material according to the present application, FIG. 9 is a surface evaluation of a film having the coating of Example 1 with the first SEM at a 60 degree tilt at 100 times magnification. The larger particles e.g,, particles 900, were polyethylene particles from the texture agent. Based on a ratio of 200 pm of film surface per, e.g., 21 millimeters (depending on size of image when printed or otherwise viewed) of picture (as described in legend 990 at the lower right corner), some of the polyethylene particles had an example, non-limiting diameter of about 110 microns,
FIG. 10 is a SEM photograph of the surface of an embodiment of a packaging material according to the present application, FIG. 10 is a surface evaluation of a film having the coating of Example 1 with the second SEM at 0 degree tilt at 100 times magnification. The larger particles (e.g., particle 1010, particle 1020, particle 1030, particle 1040) were, again, polyethylene particles from the texture agent. According to the second SEM, particle 1010 had a diameter of about 64 microns, particle 1020 had a diameter of about 69.5 microns, particle 1030 had a diameter of about 78 microns and particle 1040 had a diameter of about 73,5 microns. According to the second SEM, the polyethylene particles had a non-limiting, example average particle size of from about 70 microns to about 100 microns. Also according to the second SEM, an example, nonlimiting measurement of the distribution of polyethylene particles on this coated film surface was estimated to be from about 1,500 particles per square centimeter to about 2,000 particles per square centimeter.
FIG. 11 is a SEM photograph of the surface of an embodiment of a packaging material according to the present application, FIG. 11 is a surface evaluation of a film
WO 2015/117111
PCT/US2015/014171 having the coating of Exampie 1 with the first SEM at a 60 degree tilt at 20 times magnification. The wavy line 1160 in the upper left corner depicted the boundary between uncoated film surface and coated film surface. Based on a ratio of 2mm of film surface per, e.g., 42 millimeters (depending on size of image when printed or otherwise viewed) of picture (as described in legend 1190 in the lower right corner), an exampie, non-limiting measurement of the distribution of polyethylene particles, e.g., particles 1100, on this coated film surface was estimated to be about 4800 particles per square centimeter.
FIG. 12 is a SEM photograph of the surface of an embodiment of a packaging io material according to the present application. FIG. 12 is a surface evaluation of a film having the coating of Example 1 with the first SEM at a 60 degree tilt at 50 times magnification. Based on a ratio of 500 pm of film surface per, e,g,, 28 millimeters (depending on size of image when printed or otherwise viewed) of picture (as described in legend 1290 the lower right corner), an example, non-limiting measurement of the is distribution of polyethylene particles, e.g., particles 1200, on this coated film surface was estimated to be about 5000 particles per square centimeter.
In addition or as an alternative to microscopy, texture/roughness may be measured with a profilometer and/or based on the following “Roughness Parameters” (as reported at http://www.rubert.co.uk/Ra.htm on February 3, 2014):
WO 2015/117111
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Each and every document cited in this present application, including any cross referenced or related patent or application, and any patent application or patent to which this present application claims priority or benefit is incorporated in this present application in its entirety by this reference, unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any embodiment disclosed or claimed in this present application or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such embodiment. Further, to the extent that any meaning or definition of a term in
WO 2015/117111
PCT/US2015/014171 this present application conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this present application shall govern.
The above description, examples and embodiments disclosed are illustrative only and should not be interpreted as limiting. The present invention includes the description, examples and embodiments disclosed; but it is not limited to such description, examples or embodiments. Modifications and other embodiments will be apparent to a person of ordinary skill in the art, and all such modifications and other embodiments are intended and deemed to be within the scope of the present invention as defined by the claims.
What is claimed is as follows:
2015210692 09 Aug 2018
Claims (20)
1. A coating comprising an emulsion comprising (a) water, (b) a first particle comprising particles having an average particle size of greater than 0 but less than 10 microns and comprising acrylic beads, (c) an acrylic-based carrier and (d) a second particle comprising particles having an average particle size of from about 35 microns to about 110 microns and comprising polyamide, polyethylene, polypropylene, polytetrafluoroethylene or combinations of such, wherein the combination of the water, the first particle and the acrylic-based carrier comprises from about 75 % to about 95 % by weight of the coating and wherein the second particle comprises from about 5 % to about 25 % by weight of the coating.
2. The coating of claim 1, wherein the coating further comprises a coreactant additive in an amount from 0 % to about 5 % by weight of the coating.
3. The coating of claim 1, wherein the combination of the water, the first particle and the acrylic-based carrier comprises from about 80 % to about 90 % by weight of the coating and the second particle comprises from about 10 % to about 20 % by weight of the coating.
2015210692 09 Aug 2018
4. The coating of claim 1, wherein the combination of the water, the first particle and the acrylic-based carrier comprises from about 82 % to about 85 % by weight of the coating and the second particle comprises from about 15 % to about 18 % by weight of the coating.
5. The coating of claim 1, wherein the second particle comprises particles having an average particle size of from about 80 microns to about 110 microns.
6. The coating of claim 1, wherein the second particle comprises particles having a first particle size and a second particle size.
7. The coating of claim 1, wherein the coating is printable.
8. The coating of claim 1, wherein the coating creates an anti-glare, texture effect on a packaging material in the absence of radiation curing.
9. The coating of claim 1, wherein the coating has a viscosity of from about 50 to about 125 centipoise.
10. A packaging material comprising:
a substrate comprising metal, glass, paper, plastic or thermoplastic; and the coating of claim 1.
2015210692 09 Aug 2018
11. The packaging material of claim 10 wherein the substrate comprises a thermoplastic film.
12. The packaging material of claim 10, wherein the substrate comprises biaxially oriented polyethylene terephthalate.
13. The packaging material of claim 10 wherein the coating is printable and is flexographic printed or rotogravure printed.
14. The packaging material of claim 10, wherein the packaging material is food packaging.
15. A method of rotogravure printing the coating of claim 1 to a substrate comprising the sequential steps of (a) preparing the coating by mixing the emulsion;
(b) using a rotogravure press to apply the coating to the substrate, wherein the substrate comprises metal, glass, paper, plastic or thermoplastic; and (c) allowing the coated substrate to cure in the absence of radiation curing.
16. The method of claim 15 further comprising adding reducer/thinner to the coating as needed to adjust coating viscosity to measure from about 50 centipoise to about 125 centipoise.
2015210692 09 Aug 2018
17. The method of claim 15 further comprising adding a coreactant additive to the coating in an amount from 0 % to about 5 % by weight of the coating.
18. The method of claim 15 further comprising corona treating the substrate prior to using the rotogravure press to apply the coating to the substrate.
19. The method of claim 15 further comprising applying ink to the substrate as either a surface print or a reverse print prior to using the rotogravure press to apply the coating to the substrate.
20. The method of claim 15, wherein the rotogravure press applies the coating on a surface over the ink if surface printed or on a surface without the ink if reverse printed.
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1/11
FIG. 1
FIG. 2
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2/11
FIG. 3
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3/11
FIG. 4
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4/11
FIG.5
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5/11
FIG. 6
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6/11
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7/11
820
FIG. 8
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8/11
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9/11
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FIG. 11
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FIG. 12
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EP1944342A1 (en) * | 2006-03-15 | 2008-07-16 | Rohm and Haas Company | Aqueous compositions comprising polymeric duller particles |
US7829626B2 (en) * | 2006-03-15 | 2010-11-09 | Rohm And Haas Company | Aqueous compositions comprising polymeric duller particle |
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US3527729A (en) * | 1964-06-22 | 1970-09-08 | Minnesota Mining & Mfg | Glare-free coating compositions of elastomeric particles in an elastomeric film-former |
US20060021888A1 (en) * | 2004-07-29 | 2006-02-02 | Andre Kieran F | Packaging for golf equipment using soft touch coating |
TWI437333B (en) * | 2005-05-09 | 2014-05-11 | Sekisui Chemical Co Ltd | Liquid crystal dripping method with a sealant, upper and lower conductive material, liquid crystal display element |
US7754795B2 (en) * | 2006-05-25 | 2010-07-13 | 3M Innovative Properties Company | Coating composition |
FR2942169B1 (en) | 2009-02-13 | 2011-04-01 | Arjo Wiggins Fine Papers Ltd | MULTILAYER PRINTABLE SHEET WITH SOFT OR SOYE TOUCH AND ITS MANUFACTURING METHOD |
EP2474567B1 (en) * | 2009-09-04 | 2016-02-17 | Sumitomo Seika Chemicals Co., Ltd. | Polyolefin-based composite resin spherical particles, coating composition and coated object |
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US5518809A (en) * | 1992-09-18 | 1996-05-21 | Minnesota Mining And Manufacturing Company | Water-based transparent image recording sheet for plain paper copiers |
EP1944342A1 (en) * | 2006-03-15 | 2008-07-16 | Rohm and Haas Company | Aqueous compositions comprising polymeric duller particles |
US7829626B2 (en) * | 2006-03-15 | 2010-11-09 | Rohm And Haas Company | Aqueous compositions comprising polymeric duller particle |
Also Published As
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EP3102642A4 (en) | 2017-08-16 |
US20170166752A1 (en) | 2017-06-15 |
CA2937520C (en) | 2022-03-01 |
CN114702857A (en) | 2022-07-05 |
CN106103606A (en) | 2016-11-09 |
BR112016017590A2 (en) | 2017-08-08 |
CA2937520A1 (en) | 2015-08-06 |
MX370358B (en) | 2019-12-10 |
BR112016017590B1 (en) | 2022-05-10 |
AU2015210692A1 (en) | 2016-08-18 |
MX2016009882A (en) | 2016-11-11 |
EP3102642A1 (en) | 2016-12-14 |
EP3102642B1 (en) | 2020-07-15 |
US20190338143A1 (en) | 2019-11-07 |
ES2812805T3 (en) | 2021-03-18 |
WO2015117111A1 (en) | 2015-08-06 |
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